Azo dye compositions



Patented Sept; 30,1941

UNlTED [STA ES PATENT OFFICE;

AZO DYE CODIPOSITION S Josef Riedmair and Walter Pissler, Frankforton-the-Main-Fechenheim, and Gustav Torinus, Bad Soden, Germany, S-Signors to. .General Aniline 8; Film Corporation, New York, N. Y., a corporation of Delaware Y Nonmwing. 1 Application March '2, 1940, Serial No. 322,020. In Germany March 14, 1939' 2 Claims. (01. 8-45) Our present invention relates to a process for producing water-insoluble azodyestuffs on the fiber and to preparations for this purpose.

As is-known waterinsoluble azodyestufls can be producedon the fiber by dissolving mixtures of coupling components" andv such diazoamino 'compounds'as contain watersolubilizlng groups inthe radicle which does not take part in the dyestuff formation, in caustic alkali solutions such as a'caustic soda solution, transforming these solutions, by adding thickening agents, into the following examples are given, the parts being by weight and all temperatures in degrees a. form suitable for printing processes, imprint ing them on the fiber and finally exposing the.

viiber to the action of acid vapors at elevated temperatures. By this last step the diazbamino. compounds are split up and the diazo compound thus' formed is combined with the coupling component.

aforesaid bases,.such as tartaric acid diethylester. r

In order to further illustrate our invention,

Recently a series of new processes has been described wherein'by anew constitution-of the preparations used the pH value which is necessary for the processes of splitting up and combination is produced by a simple steaming process without the addition ofan acid. Such processes consistsubstantially inincorporating in the aforesaid preparations su'ch basesas are volatile in steam and can thereilore be removed.

by such a step. For this purpose particularly alkyl-amines and most recently hydroxylated organic bases. have been found to be suitable.

According to our invention to printing pastes,

containing thickening agents and solvents, there are added (a) such mixtures of coupling components and ofdiaz'amino compounds containing acid water'solubllizing groups in that part of their molecule which does not take part in the dyestuff formation, asallow the splitting oil of the diazoamino compound aswell'as the dyestuil formation in a slightlyacid to neutral medium, (b) volatile bases such asalkylamines or hydroxylated organic bases, and (0) salt solutions obtained by neutralizing the aforesaid volatile bases with a substance acting as an acid.

By this step an essential increase of the yield of dyestufi without injuring the stability of the printing pastes is obtainable. As suitable acids 4 there may be mentioned weak, inorganic acids such as phosphoric acid and organic acids such as sulfocyanic, formic, acetic, oxalic, tartaric and glycollic acid. Instead of such salts, derivatives of the acids may be used, which are easily converted into the salts in the presence of the A neutral starch-tragacanth thickener 550 are worked v up in the normal manner to a printing paste, the material is printed therewith,

. of sarcoslne 8.1 Glycol-monoethyl ether 50 Dimethyiaminobutanone 1-20 Tartaric acid diethylester 20 Water 230 dried at 50 to 60f and steamed for about 5 minutes in the Mather'Platt, rinsed and soaped. A'strong yellow print is obtained of an essentially increased tinetorial power as compared with a print prepared without the addition of the formic acid .salt of diethyloxethylamine. The'pastes are very stable. a

Example 2 l I Parts 1 benzoylamino-4 benzoylacetylamino-Z.5

dimethoxybenzene 12.1 The diazoamino compound fromdiamtized 4-chloro-2-anisidine and the sodium salt A neutral starch-tragacanth thickener .550

are worked up in the normal manner to a printing paste and the material is printed therewith as described in Example 1. In-this manner clear I gold-yellow prints are obtained. The printing pastes are excellently-stable.

With the same good result the tartaric acid diethylester may be replaced by the glycollic acid ester of 3.-m etho'xy-1-butanol.

When working without such an addition the yield of dyestuii is very minor.

A mixture of z-hydroxycarbazole-ii-carbox- Example 3 Parts are worked up to a printing paste and the material is printed therewith as described in Example 1. In this manner bright and strong brown prints are obtained being superior as to tinctorial power in comparison with prints produced without the addition of acetic acid diethyloxethylamine.

Example 4 With a printing paste, consisting of Parts l-acetoacetylamino-4-chloro 2.5 dimethoxsbenzene I The diazoamino compound from diazotized' 5-chloro-2-toluidine and the sodium salt of methyltaurine 16.8 Glycol monoethyl ether 50 n-Propylaminoethanole 100 An aqueous solution obtained by slightly warming parts of N-propylaminoethanol with an aqueous solution of 14.8 parts of ammonium sulfocyanate until the formation of Nvpropylamino-ethanol-sulfocyanate 50 Water 220 A neutral starch-tragacanth thickener 550 theflber is printed as described in Example 1.

In this manner a bright greenish yellow print is obtained whereas. without the addition of N propylaminoethanol sulfocyanat'e essentially less strong shades are obtained. The printing paste is stable for some weeks.

Example 5 Parts 2-acetoacetylamino-5-methoxy-6-ethoxybenzthiazole, 22.3 The diazoamlno compound from dlazotized 4-chloro-2-toluidine and the sodium salt or sarcosine i 19.1 Glycol monoethyl ether 50 Dimethylamino-ethanoie 120 'rartaric acid diethylester 20 Water 220 A neutral starch-tragacanth thickener"-.. 550

' described in Example 1.

are worked up in the normal manner to a print-- in: paste and a tissue is printed therewith as r A- bright and strong gold-yellow print is ob ained whereas without the addition of tartaric acid diethylester only very slight shades are obtained. The stability ot,

the printing paste is excellent.

Example 6 Parts ,A mixture or 2'-hydroxy-3'-naphthoylamino-i 2-methoxybenzene and the diazoaminocompound vfrom diazotized 4-chloro-2- amino-l-methoxybenezene and the sodium salt of sarcosine '8 Glycol monoethyl ether 50 Diethyloxethylamine y 100 Tartaric acid diethylester--. 20 Water s 200 A neutral starch-tragacanth thickener- 550 are made up to a printing paste and according to Example 1 the is printed therewith. In this manner a strong'red print is obtained, which is superior as to tinctorial power in comparison with a print made without the 'addition'oi tartaric acid diethylester. printing paste is excellent.

The stability of the We claim:

1. A process for producing waterinsoluble azo- .dyestuiis on the flber which consists in addin to gprlnm pa tes including thickening agents and solvents such mixtures of coupling components and of diazoamino compounds containing acid watersolubilizing groups in that part of their molecule which does not take part in the dyestufl formation. as allow the splitting 011 o! the diazoamino compound as well as the dyestufl formation in a slightly acidto neutral medium, volatile bases, and salt solutions ob-- tained by neutralizing the aforesaid volatile bases with a substance acting as an acid.

2. Preparations including besides thickening agents and solvents such mixtures of coupling components and of diazoamino compounds containing acid watersolubilizing groups in that part or their molecule which does not take part in the dyestufl formation, as allow the splitltng oil of the diazoamino compound as well as the dyestufl formation in a slightly acid to neutral medium, volatile .bases, and salt solutions obtained by neutralizing the aforesaid volatile bases .with a substance acting as an acid.

JOSEF RIEDMAIRI. WALTER PiissLER. aus'rsv 'ronmus. 

